Method for producing resin composition

ABSTRACT

It is an object of the present invention to provide a method for obtaining a resin composition in which coloration is suppressed. According to an embodiment, provided is a method for producing a resin composition, including: (a) obtaining a resin by polymerization of a resin raw material containing a compound represented by formula (1) below and (b) obtaining a resin composition by mixing an additive into the resin, wherein a polymerization temperature T 1  in step (a) falls within the range of 230° C.&lt;T 1 &lt;250° C., and a mixing temperature T 2  in step (b) falls within the range of 250° C.≤T 2 &lt;280° C.

TECHNICAL FIELD

The present invention relates to a method for producing a resincomposition containing a resin having a specific fluorene structure.

BACKGROUND ART

Optical glasses or optical transparent resins are used as materials foroptical elements used for optical systems of various cameras such ascameras, film integrated cameras, and video cameras. There are varioustypes of optical glasses which have excellent properties such as heatresistance, transparency, dimensional stability, chemical resistance,etc. and varieties of refractive indices and Abbe numbers, but suchoptical glasses have problems of poor forming fabricability and lowproductivity, in addition to high material cost. In particular,processing into aspherical lenses that are used for aberrationcorrection requires an exceptionally high level of technique and highcost, which are therefore serious obstacles for practical use.

In contrast to the aforementioned optical glasses, optical transparentresins, particularly, optical lenses consisting of thermoplastictransparent resins have advantages that such optical lenses can bemass-produced by injection molding, and aspherical lenses also can beeasily produced, and are therefore used currently as camera lenses.Examples of the optical transparent resins include polycarbonateconsisting of bisphenol A, polymethyl methacrylate, or amorphouspolyolefin. Further, polycarbonate resins are particularly used also assheets or films for optical applications. Sheets and films consisting ofpolycarbonate resins have high transparency and heat resistance, and aretherefore used suitably for front protective sheets, light guidingsheets, or the like, of liquid crystal display devices.

However, polycarbonate resins consisting of bisphenol A have adisadvantage of high birefringence, and therefore the applicationsthereof are constrained. In particular, in applications for mobile phonecameras and digital cameras in recent years, there is a growing demandfor resin materials having high imaging performance and lowbirefringence, with an increase in resolution due to an increase in thenumber of pixels. Patent Literature 1 discloses that use of dicarboxylicacid having a fluorene structure as a raw material for polyester resinsis effective for reducing the birefringence.

Aiming at further excellent materials, a resin having various excellentoptical properties such as high refractive index and low Abbe number hasbeen developed (Patent Literature 2). However, in recent years, whileelectronic devices such as digital cameras, smartphones, and tablets arewidely adopted, and various models are put on the market, functions ofcameras mounted on such devices are being progressively enhanced (suchas higher pixel density and lower F value). In order to precisely moldmembers such as lenses, sheets, or films, a resin having not onlyoptical properties but also less coloration is desired. Further, withthe enhancement of functions of the devices, sheets or films havingexcellent shapability are also desired.

CITATION LIST Patent Literature

Patent Literature 1: Japanese Patent Laid-Open No. 2013-64119

Patent Literature 2: International Publication No. 2014/073496

SUMMARY Technical Problem

In view of the aforementioned problems, it is an object of the presentinvention to provide a method for obtaining a resin composition in whichcoloration is suppressed.

Solution to Problem

Involvement of vinyl groups is known as one of the causes for resincoloration (for example, Japanese Patent Laid-Open No. 2004-323837).Further, the inventors have found that aliphatic terminal OH groups(that is, hydroxyalkyl groups located at terminals of compounds) in theresin composition are also involved in the resin coloration. As a resultof extensive studies, the inventors have found that the content of vinylgroups and the amount of aliphatic terminal OH groups contained in theresin composition can be reduced by performing polymerization reactionand mixing an additive thereinto at a predetermined temperature using adihydroxy compound having a specific fluorene structure as a rawmaterial, and have achieved the present invention. The present inventionis, for example, as follows.

[1] A method for producing a resin composition comprising:

(a) obtaining a resin by polymerization of a resin raw materialcontaining a compound represented by formula (1) below:

wherein

R₁ and R₂ are each independently selected from a hydrogen atom, an alkylgroup having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, acycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and ahalogen atom;

each X is independently an optionally branched alkylene group having 2to 6 carbon atoms; and

each n is independently an integer of 1 to 5; and

(b) obtaining a resin composition by mixing an additive into the resin,wherein a polymerization temperature T1 in step (a) falls within therange of 230° C.<T1<250° C., and

a mixing temperature T2 in step (b) falls within the range of 250°C.≤T2<280° C.

[2] The method according to [1], wherein the polymerization is performedunder a pressure of 1 Torr or less.

[3] The method according to [1] or [2], wherein X is ethylene.

[4] The method according to any of [1] to [3], wherein n is 1.

[5] The method according to any of [1] to [4], wherein the compoundrepresented by formula (1) is selected from the group consisting of9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.

[6] The method according to any of [1] to [5], wherein the resin furthercontains a structural unit derived from a compound represented byformula (2) below:

wherein

R₆ and R₇ are each independently selected from a hydrogen atom, an alkylgroup having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, acycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and ahalogen atom;

each Y is independently an optionally branched alkylene group having 2to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, oran arylene group having 6 to 10 carbon atoms;

W is a single bond or

wherein R₈, R₉, and R₁₄ to R₁₇ are each independently selected from ahydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an arylgroup having 6 to 10 carbon atoms; R₁₀ and R₁₁ are each independentlyselected from a hydrogen atom and an alkyl group having 1 to 5 carbonatoms; R₁₂ and R₁₃ are each independently selected from a hydrogen atom,an alkyl group having 1 to 5 carbon atoms, and a phenyl group; and Z′ isan integer of 3 to 11; and

p and q are each independently an integer of 0 to 5.

[7] The method according to [6], wherein p and q are 0, and

W is:

wherein R₈ and R₉ are as defined in [6].

[8] The method according to [6], wherein the compound represented byformula (2) is bisphenol A.

[8-1] The method according to any one of [l] to [8], wherein the ¹H-NMRspectrum of the resin composition satisfies a relationship of:

${\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.75\mspace{14mu}{to}\mspace{14mu} 4.69\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 7.83\mspace{14mu}{to}\mspace{14mu} 7.65\mspace{14mu}{ppm}} \times 100} \leq {0.5.}$

[9] The method according to any of [1] to [5], wherein the resin furthercontains a structural unit derived from a compound represented byformula (3) below:

wherein

each Z is independently an optionally branched alkylene group having 2to 6 carbon atoms; and

each m is independently an integer of 1 to 5.

[10] The method according to [9], wherein Z is ethylene.

[11] The method according to [9] or [10], wherein m is 1.

[12] The method according to [9], wherein the compound represented byformula (3) is 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalenc.

[12-1] The method according to any one of [9] to [12], wherein a molarratio of the repeating unit derived from the compound represented byformula (1) to the repeating unit derived from the compound representedby formula (3) in the resin is 20:80 to 99:1.

[12-2] The method according to any one of [9] to [12-1], wherein the¹H-NMR spectrum of the resin composition satisfies a relationship of:

${\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.75\mspace{14mu}{to}\mspace{14mu} 4.69\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}} \times 100} \leq 1.0$or${\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.59\mspace{14mu}{to}\mspace{14mu} 4.55\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}} \times 100} \leq {1.0.}$

[13] The method according to any one of [1] to [12-3], wherein the resinis selected from the group consisting of a polycarbonate resin, apolyester resin, and a polyester carbonate resin.

[14] The method according to [13], wherein the resin is a polycarbonateresin.

[14-1] The method according to any one of [1] to [14], having a meltvolume rate (MVR) of the resin composition of 30 cm³/10 min or more.

[14-2] The method according to any one of [1] to [14-1], wherein theresin composition has a yellowness of less than 20.

Advantageous Effects of Invention

The present invention can provide a method for obtaining a resincomposition in which coloration is suppressed.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1a, 1b and 1c are ¹H-NMR charts of a resin composition produced inExample 1.

FIGS. 2a and 2b are ¹H-NMR charts of a resin composition produced inExample 2.

FIGS. 3a and 3b are ¹H-NMR charts of a resin composition produced inExample 3.

FIGS. 4a and 4b are ¹H-NMR charts of a resin composition produced inExample 4.

FIGS. 5a and 5b are ¹H-NMR charts of a resin composition produced inComparative Example 1.

FIGS. 6a and 6b are ¹H-NMR charts of a resin composition produced inComparative Example 2.

DESCRIPTION OF EMBODIMENTS

Hereinafter, embodiments of the present invention will be described indetail.

A method for producing a resin composition according to the presentinvention comprises: (a) obtaining a resin (hereinafter also referred toas resin (A)) by polymerization of a resin raw material containing acompound represented by formula (1) below:

wherein

R₁ and R₂ are each independently selected from a hydrogen atom, an alkylgroup having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, acycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and ahalogen atom;

each X is independently an optionally branched alkylene group having 2to 6 carbon atoms; and

each n is independently an integer of 1 to 5; and

(b) obtaining a resin composition by mixing an additive into the resin.

Further, in the aforementioned method, a polymerization temperature T1in step (a) falls within the range of 230° C.<T1<250° C., and a mixingtemperature T2 in step (b) falls within the range of 250° C.≤T2<280° C.

In this way, a resin that contains a repeating unit having a specificfluorene structure and is obtained by polymerization at a predeterminedtemperature is mixed with an additive at a predetermined temperature toobtain a resin composition having less coloration. Such a resincomposition having less coloration is suitable as a material forprecision members and members required to have transparency. Therefore,the resin composition of the present invention can be suitably used as amaterial for sheets and films used for optical lenses in digitalcameras, smartphones, tablets, and the like, and front protective sheets(films), light guiding sheets (films), and the like, of liquid crystaldisplay devices. Further, the resin composition is also suitable as amaterial for sheets and films having patterns on their surfaces.

Although the reason why the coloration of the resin composition obtainedby the method of the present invention is suppressed is not clear, it isinferred as follows.

Generally, higher polymerization temperature is preferable in that itleads to good reactivity and short reaction time to reach a desiredmolecular weight. Meanwhile, monomers used as the resin raw materials inthe present invention have a structure containing primary alcohol groupsat terminals, and have a problem that vinyl groups that cause colorationtend to be produced due to dehydration reaction proceeding from themonomers under high temperature. Further, even after the polymerizationreaction, dehydration reaction of terminal OH groups and pyrolysisreaction of oxygen atoms with alkylene chain moieties (—O—X—) (forexample, cleavage reaction such as intramolecular hydrogen transferreaction) gradually proceed under high temperature, and thus vinylgroups tend to be produced. Therefore, it is theoretically consideredthat resins of higher quality are obtained by reducing the reactiontemperature to a comparatively low temperature. By the same reason, itis considered that the mixing (extrusion and kneading) with the additiveis preferably performed at a comparatively low temperature in order toprevent the progress of the dehydration reaction and the pyrolysisreaction. However, the resin of the present invention is considered tohave a structure in which shear stress is easily converted to heat, andthus it is inferred that the production of vinyl groups, that is, thedehydration reaction from the OH terminals and the pyrolysis reaction ofpolymer chains can be suppressed even at a comparatively hightemperature by increasing the fluidity of the resin for mixing.

Further, mixing time is generally shorter than polymerization time, butshear stress applied on the resin is larger in mixing. In the presentinvention, the mixing with the additive is performed at a further highertemperature than the polymerization temperature, so that the fluidity ofthe resin can be increased. It is inferred that, as a result of theabove, the occurrence of shear heating is reduced to suppressintramolecular heat transfer reaction or the like, and the occurrence ofcoloring components derived from aromatic rings can be prevented.

Further, polymerization and mixing can be performed at such acomparatively high temperature, and thereby the production of compoundshaving aliphatic terminal OH groups also can be suppressed. According tothe studies by the inventors, it has turned out that the lower thepolymerization temperature and the temperature at which the additive ismixed, the amount of compounds having aliphatic terminal OH groups to beproduced increases. As the amount of aliphatic terminal OH groups in theresin composition increases, the hydrolysis resistance deteriorates, andproducts produced by hydrolysis reaction cause yellowing of the resin.However, according to the method of the present invention, it isconsidered that the production of compounds having aliphatic terminal OHgroups can be suppressed because the polymerization reaction and themixing with the additive are performed at a comparatively hightemperature.

Thus, according to the method of the present invention, the productionof compounds having vinyl groups and compounds having aliphatic terminalOH groups can be suppressed at a comparatively high temperature, andtherefore good reactivity can be maintained in the polymerizationreaction.

1. Resin (A)

First, the constitution of resin (A) will be described.

In formula (1), R₁ and R₂ are each independently selected from ahydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxylgroup having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an arylgroup having 6 to 20 carbon atoms, an aryloxy group having 6 to 20carbon atoms, and a halogen atom. Among these, a hydrogen atom, an alkylgroup having 1 to 12 carbon atoms, or an aryl group having 6 to 12carbon atoms is preferable, a hydrogen atom, a methyl group, an ethylgroup, a propyl group, an isopropyl group, a butyl group, an isobutylgroup, a sec-butyl group, a tert-butyl group, a cyclohepta group, acyclopropyl group, or a phenyl group is more preferable, a hydrogenatom, a methyl group, or a phenyl group is particularly preferable, anda hydrogen atom or a phenyl group is most preferable.

Each X is independently an optionally branched alkylene group having 2to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbonatoms, more preferably an ethylene group or a propylene group,particularly preferably an ethylene group.

Each n is independently an integer of 1 to 5, preferably an integer of 1to 3, more preferably an integer of 1 to 2, particularly preferably 1.

Examples of the compound represented by formula (1) include9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene,9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene,9,9-bis(4-hydroxy-3-ethylphenyl)fluorene,9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, and9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene. Above all,9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (hereinafter also referred toas BPEF) or 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene(hereinafter also referred to as BPPEF) is suitably used.

The ratio of the repeating unit derived from the compound represented byformula (1) in resin (A) is preferably 40 mol % or more, more preferably50 mol % or more, further preferably 80 mol % or more, particularlypreferably 90 mol % or more, most preferably 100 mol %, based on allrepeating units constituting resin (A). Resin (A) may contain arepeating unit other than the repeating unit derived from the compoundrepresented by formula (1).

Examples of the other repeating unit include a repeating unit derivedfrom a compound represented by formula (2) below:

In this case, resin (A) is a resin obtained by polymerization of a resinraw material containing the compound represented by formula (1) and thecompound represented by formula (2). That is, according to oneembodiment, resin (A) contains a repeating unit derived from thecompound represented by formula (1) and a repeating unit derived fromthe compound represented by formula (2).

In formula (2), R₆ and R₇ are each independently selected from ahydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxylgroup having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an arylgroup having 6 to 20 carbon atoms, an aryloxy group having 6 to 20carbon atoms, and a halogen atom. Among these, a hydrogen atom, an alkylgroup having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 20carbon atoms, and an aryl group having 6 to 15 carbon atoms arepreferable, a hydrogen atom, a methyl group, an ethyl group, a propylgroup, a butyl group, a cyclohexyl group, and a phenyl group are morepreferable, and a hydrogen atom, a methyl group, and a phenyl group areparticularly preferable.

Each Y is independently an optionally branched alkylene group having 2to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, oran arylene group having 6 to 10 carbon atoms. Among these, an alkylenegroup having 2 to 6 carbon atoms is preferable, ethylene or propylene ismore preferable, and ethylene is particularly preferable.

W is a single bond or selected from the group consisting of:

wherein R₈, R₉, and R₁₄ to R₁₇ are each independently selected from ahydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an arylgroup having 6 to 10 carbon atoms; R₁₀ and R₁₁ are each independentlyselected from a hydrogen atom and an alkyl group having 1 to 5 carbonatoms; R₁₂ and R₁₃ are each independently selected from a hydrogen atom,an alkyl group having 1 to 5 carbon atoms, and a phenyl group; and Z′ isan integer of 3 to 1.

W is preferably a single bond or

more preferably

particularly preferably

R₈, R₉, and R₁₄ to R₁₇ are preferably an alkyl group having 1 to 10carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogenatom, more preferably a hydrogen atom, a methyl group, or a phenylgroup, particularly preferably a methyl group.

R₁₀ and R₁₁ are preferably a hydrogen atom or a methyl group, morepreferably a hydrogen atom.

R₁₂ and R₁₃ are preferably each independently a hydrogen atom.

Z′ is preferably 3 to 10, more preferably 3 to 5, particularlypreferably 5.

p and q are each independently an integer of 0 to 5, preferably 0 to 3,more preferably 0 or 1, and it is particularly preferable that both of pand q are 0.

Specific examples of the compound represented by formula (2) include2,2-bis(4-hydroxyphenyl)propane [=bisphenol A],1,1-bis(4-hydroxyphenyl)-1-phenyl ethane [=bisphenol AP],2,2-bis(4-hydroxyphenyl)hexafluoropropane [=bisphenol AF],2,2-bis(4-hydroxyphenyl)butane [=bisphenol B],bis(4-hydroxyphenyl)diphenylmethane [=bisphenol BP],bis(4-hydroxy-3-methylphenyl)propane [=bisphenol C],1,1-bis(4-hydroxyphenyl)ethane [bisphenol E],bis(4-hydroxyphenyl)methane [=bisphenol F], bis(2-hydroxyphenyl)methane,2,2-bis(4-hydroxy-3-isopropylphenyl)propane [=bisphenol G],1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene [=bisphenol M],bis(4-hydroxyphenyl)sulfone [=bisphenol S],1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene [=bisphenol P],bis(4-hydroxy-3-phenylphenyl]propane [=bisphenol PH],1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane [=bisphenol TMC],1,1-bis(4-hydroxyphenyl)cyclohexane [=bisphenol Z],1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (bisphenol OCZ), and4,4-bisphenol. Among these, bisphenol A, bisphenol M, bisphenol C,bisphenol Z, and bisphenol TMC are preferable, and bisphenol A is morepreferable.

The total ratio of the repeating unit derived from the compoundrepresented by formula (1) and the repeating unit derived from thecompound represented by formula (2) is preferably 40 mol % or more, morepreferably 50 mol % or more, further preferably 80 mol % or more,particularly preferably 90 mol % or more, most preferably 100 mol %,based on all repeating units constituting resin (A). Resin (A) maycontain a repeating unit other than the repeating unit derived from thecompound represented by formula (1) and the repeating unit derived fromthe compound represented by formula (2).

The molar ratio of the repeating unit derived from the compoundrepresented by formula (1) to the repeating unit derived from thecompound represented by formula (2) is preferably 20:80 to 99:1, morepreferably 30:70 to 98:2, particularly preferably 40:60 to 95:5.

Examples of the other repeating unit that may be contained in resin (A)include a repeating unit derived from a compound represented by formula(3) below.

In this case, resin (A) is a resin obtained by polymerization of a resinraw material containing the compound represented by formula (1) and thecompound represented by formula (3). That is, according to oneembodiment, resin (A) contains a repeating unit derived from thecompound represented by formula (1) and a repeating unit derived fromthe compound represented by formula (3).

In formula (3), each Z is independently an optionally branched alkylenegroup having 2 to 6 carbon atoms, preferably an alkylene group having 2to 4 carbon atoms, more preferably an ethylene group or a propylenegroup, particularly preferably an ethylene group.

Each m is independently an integer of 1 to 5, preferably an integer of 1to 3, more preferably an integer of 1 to 2, particularly preferably 1.

Examples of the compound represented by formula (3) include2,2′-bis(hydroxymethoxy)-1,1′-binaphthalene,2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene,2,2′-bis(3-hydroxypropyloxy)-1,1′-binaphthalene, and2,2′-bis(4-hydroxybutoxy)-1,1′-binaphthalene. Above all,2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene (hereinafter also referredto as BHEBN) is suitably used.

The total ratio of the repeating unit derived from the compoundrepresented by formula (1) and the repeating unit derived from thecompound represented by formula (3) is preferably 40 mol % or more, morepreferably 50 mol % or more, further preferably 80 mol % or more,particularly preferably 90 mol % or more, most preferably 100 mol %,based on all repeating units constituting resin (A). Resin (A) maycontain a repeating unit other than the repeating unit derived from thecompound represented by formula (1) and the repeating unit derived fromthe compound represented by formula (3).

The molar ratio of the repeating unit derived from the compoundrepresented by formula (1) to the repeating unit derived from thecompound represented by formula (3) is preferably 20:80 to 99:1, morepreferably 30:70 to 95:5, particularly preferably 40:60 to 90:10.

<Other Components>

Resin (A) may contain a repeating unit derived from a compound otherthan the compounds of formulas (1) to (3). The amount thereof isdesirably 20 mol % or less, further desirably 10 mol % or less, per 100mol % in total of the repeating units derived from the compoundsrepresented by formulas (1) to (3). When the amount falls within thisrange, a high refractive index is maintained.

Examples of the repeating unit that may be further contained thereininclude repeating units derived from aliphatic dihydroxy compounds suchas ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol,1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, and 1,6-hexanediol;alicyclic dihydroxy compounds such as 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol,tricyclodecanedimethanol, pentacyclopentadecanedimethanol,2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol,2,3-norbornanedimethanol, 2,5-norbornanedimethanol, and1,3-adamantanedimethanol; and aromatic bisphenols such as2,2-bis(4-hydroxyphenyl)propane [=bisphenol A],2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,2,2-bis(4-hydroxy-3,5-diethylphenyl)propane,2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane,2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,2,2-bis(4-hydroxyphenyl)pentane, 2,4′-dihydroxy-diphenylmethane,bis(4-hydroxyphenyl)methane, bis(4-hydroxy-5-nitrophenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyphenyl)pentane,1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone,2,4′-dihydroxydiphenylsulfone, bis(4-hydroxyphenyl) sulfide,4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenylether, 9,9-bis(4-hydroxyphenyl)fluorene, and9,9-bis(4-hydroxy-2-methylphenyl)fluorene.

2. Steps of Producing Resin Composition

Subsequently, each step of producing the resin composition will besequentially described.

(1) Production Step (a)

In step (a), a resin material containing the compound represented byformula (1) is polymerized to obtain resin (A). The polymerizationtemperature T1 in step (a) falls within the range of 230° C.<T1<250° C.The polymerization temperature T1 is preferably about 240° C. and ispreferably within the range, for example, of 235° C.≤T1≤245° C., 237°C.≤T1≤243° C., or 238° C.≤T1≤242° C.

The type of the resin of the present invention is not specificallylimited, but polycarbonate resins, polyester resins, or polyestercarbonate resins are preferable, and polycarbonate resins are morepreferable. Further, such a resin may have any structure such as random,block, and alternating copolymer. Hereinafter, a polycarbonate resinwill be described particularly in detail.

A polycarbonate resin is a resin in which each repeating unitconstituting the resin is bonded via a carbonate bond. In the case wherethe resin containing the repeating unit derived from the compoundrepresented by formula (1) in the present invention is such apolycarbonate resin, it can be produced by a melt polycondensationmethod, using the compound represented by formula (1) and a carbonateprecursor such as diester carbonate as raw materials, in the presence ofa basic compound catalyst, a transesterification catalyst, or a mixedcatalyst consisting of both of them, or in the absence of a catalyst.

Examples of the diester carbonate used for this reaction includediphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate,m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutylcarbonate, and dicyclohexyl carbonate. Among these, diphenyl carbonateis particularly preferable. The diester carbonate is preferably used ata molar ratio of 0.97 to 1.20, further preferably a molar ratio of 0.98to 1.10, per 1 mol in total of dihydroxy compounds. In the case wherethe amount of diester carbonate is out of the range, problems that theresin does not reach a desired molecular weight, and unreacted rawmaterials remain the resin, resulting in a reduction in opticalproperties, for example, can occur.

Examples of the basic compound catalyst particularly include alkalimetal compounds, alkaline earth metal compounds, and nitrogen-containingcompounds.

Examples of the alkali metal compounds include organic acid salts,inorganic salts, oxides, hydroxides, hydrides, or alkoxides, of alkalimetals. Specifically, sodium hydroxide, potassium hydroxide, cesiumhydroxide, lithium hydroxide, sodium hydrogen carbonate, sodiumcarbonate, potassium carbonate, cesium carbonate, lithium carbonate,sodium acetate, potassium acetate, cesium acetate, lithium acetate,sodium stearate, potassium stearate, cesium stearate, lithium stearate,sodium borohydridc, sodium borophenylate, sodium benzoate, potassiumbenzoate, cesium benzoate, lithium benzoate, disodium hydrogenphosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate,disodium phenylphosphate, disodium salt, dipotassium salt, dicesiumsalt, or dilithium salt of bisphenol A, sodium salt, potassium salt,cesium salt, or lithium salt of phenol, or the like, is used therefor.Among these, sodium hydrogen carbonate is preferable, since it has highcatalytic activity, and inexpensive sodium hydrogen carbonate with highpurity is distributed.

Examples of the alkaline earth metal compounds include organic acidsalts, inorganic salts, oxides, hydroxides, hydrides, or alkoxides, ofalkaline earth metal compounds. Specifically, magnesium hydroxide,calcium hydroxide, strontium hydroxide, barium hydroxide, magnesiumhydrogen carbonate, calcium hydrogen carbonate, strontium hydrogencarbonate, barium hydrogen carbonate, magnesium carbonate, calciumcarbonate, strontium carbonate, barium carbonate, magnesium acetate,calcium acetate, strontium acetate, barium acetate, magnesium stearate,calcium stearate, calcium benzoate, magnesium phenyl phosphate, or thelike, is used therefor.

Examples of the nitrogen-containing compounds include quaternaryammonium hydroxides and salts thereof, and amines. Specifically,quaternary ammonium hydroxides having an alkyl group, an aryl group, orthe like, such as tetramethylammonium hydroxide, tetraethylammoniumhydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide,and trimethylbenzylammonium hydroxide; tertiary amines such astriethylamine, dimethylbenzylamine, and triphenylamine; secondary aminessuch as diethylamine and dibutylamine; primary amines such aspropylamine and butylamine; imidazoles such as 2-methylimidazole,2-phenylimidazole, and benzoimidazole; or bases or basic salts such asammonia, tetramethylammonium borohydride, tetrabutylammoniumborohydride, tetrabutylammonium tetraphenylborate, andtetraphenylammonium tetraphenylborate are used therefor.

As the transesterification catalyst, salts such as zinc, tin, zirconium,and lead are preferably used, and these can be used individually or incombination.

As the transesterification catalyst, zinc acetate, zinc benzoate, zinc2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II)acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide,dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate,zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate, or thelike, is specifically used.

Such a catalyst is used at a molar ratio of 1×10⁻⁹ to 1×10⁻³, preferablyat a molar ratio of 1×10⁻⁷ to 1×10⁻⁴, per 1 mol in total of dihydroxycompounds.

Two or more types of catalysts may be used in combination. Further, thecatalyst may be added as it is or may be added after being dissolved ina solvent such as water and phenol.

In the melt polycondensation method, melt polycondensation is performedby transesterification reaction using the raw materials and the catalystdescribed above, under heating and normal pressure or reduced pressure.That is, it is preferable to start the reaction at normal temperatureand normal pressure and then to gradually raise the temperature andreduce the pressure while removing by-products. The pressure reductiondegree in the final stage of the reaction is preferably 100 to 0.01Torr, more preferably 50 to 0.01 Torr, particularly preferably 5 to 0.1Torr, most preferably 1 Torr or less (for example, 1 to 0.01 Torr).

Here, the final stage of the reaction is a stage of performingpolymerization reaction under reduced pressure (for example, 100 to 0.01Torr) after performing transesterification reaction by melting the rawmaterials. The polymerization temperature T1 in the present invention isa temperature at the final stage of the reaction.

It is considered that compounds having vinyl groups tend to have lowboiling point, and the pressure reduction degree at the final stage ofthe polymerization reaction affects the remaining amount of compoundshaving vinyl groups in the reaction system. That is, the lower thepressure, the remaining amount of compounds having vinyl groups in thereaction system can be reduced.

The catalyst may be present from the beginning of the reaction togetherwith the raw materials or may be added in the course of the reaction.

The melt polycondensation reaction may be performed continuously or maybe performed batchwise. The reactor used for performing the reaction maybe a vertical reactor equipped with an anchor-type stirring blade, aMaxblend stirring blade, a helical ribbon-type stirring blade, or thelike, a horizontal reactor equipped with a paddle blade, a latticeblade, a spectacle-shaped blade, or the like, or an extruder-typereactor equipped with a screw. Further, these reactors are suitably usedappropriately in combination, in consideration of the viscosity of thepolymer.

In this method for producing a polycarbonate resin, the catalyst may beremoved or inactivated after the completion of the polymerizationreaction, in order to maintain thermostability and hydrolytic stability,but is not necessarily inactivated. In the case of inactivating thecatalyst, a known method for inactivating a catalyst by adding an acidicsubstance can be suitably performed. Specifically, as the acidicsubstance, esters such as butyl benzoate; aromatic sulfonic acids suchas p-toluenesulfonic acid; aromatic sulfonic acid esters such as butylp-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids suchas phosphorous acid, phosphoric acid, and phosphonic acid; phosphiteesters such as triphenyl phosphite, monophenyl phosphite, diphenylphosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butylphosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctylphosphite; phosphate esters such as triphenyl phosphate, diphenylphosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate,and monooctyl phosphate; phosphonic acids such as diphenylphosphonicacid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonicacid esters such as diethylphenylphosphonate; phosphines such astriphenylphosphine and bis(diphenylphosphino)ethane; boric acids such asboric acid and phenylboric acid; aromatic sulfonates such astetrabutylphosphonium salt of dodecylbenzenesulfonic acid; organichalides such as stearic acid chloride, benzoyl chloride, andp-toluenesulfonic acid chloride; alkyl sulfates such as dimethylsulfate; and organic halides such as benzyl chloride are suitably used.In view of effects of the deactivator and the stability to the resin,p-toluene or butyl sulfonate is particularly preferable. Such adeactivator is used at 0.01 to 50 times by mole, preferably 0.3 to 20times by mole, the amount of the catalyst. When the amount of thedeactivator is less than 0.01 times by mole the amount of the catalyst,the inactivation effect is insufficient, which is not preferable.Further, when the amount of the deactivator is more than 50 times bymole the amount of the catalyst, the heat resistance of the resin isreduced, and the molded product tends to be colored, which is notpreferable.

The aforementioned deactivator can be added by kneading and may be addedcontinuously or batchwise. The temperature during kneading is preferably200 to 350° C., more preferably 230 to 300° C., particularly preferably250 to 270° C. As a kneader, an extruder is suitably used in the case ofcontinuous addition, and a Labo Plastomill and a kneader are suitablyused in the case of batch addition. Examples of the extruder includesingle-screw extruders, twin-screw extruders, and multi-screw extruders.In the extruder, a gear pump or the like for stably quantifying theoutput rate of the resin can be appropriately provided. The atmosphericpressure in melt-kneading the deactivator is not particularly limited,and normal pressure or reduced pressure, for example, a pressure ofnormal (760 mmHg) to 0.1 mmHg is preferable, in order to preventoxidation and remove decomposed products and components having a lowboiling point such as phenols. The extruder may be ventilated ornon-ventilated but is preferably ventilated for improving the quality ofextruded products. The pressure at the vent port (vent pressure) may benormal or reduced pressure but may be, for example, a pressure of normal(760 mmHg) to 0.1 mmHg, preferably a pressure of about 100 to 0.1 mmHg,more preferably a pressure of about 50 to 0.1 mmHg, in order to preventoxidation and remove decomposed products and components having a lowboiling point such as phenols. Further, hydrogenation and dehydrationmay be performed for the purpose of reducing the components having a lowboiling point such as phenols more efficiently.

The deactivator may be kneaded immediately after the completion of thepolymerization reaction or may be kneaded after pelletizing thepolymerized resin. Further, additives (such as an antioxidant, a releaseagent, an ultraviolet absorber, a flow modifier, a crystal nucleatingagent, an enhancer, a dye, an antistatic agent, or an antibacterialagent) other than the deactivator can be added by the same method.

After the catalyst is inactivated (in the case where the deactivator isnot added, after the completion of the polymerization reaction), a stepof removing low boiling point compounds in the polymer by dehydration ata pressure of 0.1 to 1 mmHg and a temperature of 200 to 350° C. may beprovided. The temperature in the dehydration removal is preferably 230to 300° C., more preferably 250 to 270° C. For this step, a horizontalapparatus equipped with a stirring blade having excellent surfacerenewal performance such as a paddle blade, a lattice blade, and aspectacle-shaped blade, or a thin film evaporator is suitably used.

The polycarbonate resin is required to contain foreign matter as littleas possible, and filtration of the molten raw materials, filtration ofthe catalyst solution, or the like is suitably performed. The mesh ofthe filter is preferably 5 μm or less, more preferably 1 μm or less.Further, filtration of the resin to be produced using a polymer filteris suitably performed. The mesh of the polymer filter is preferably 100μm or less, more preferably 30 μm or less. Further, a step of collectingresin pellets of course needs to be carried out in a low dustenvironment, where class 6 or less is preferable, and class 5 or less ismore preferable.

Further, the average molecular weight Mw of the polycarbonate resin interms of polystyrene is preferably 20000 to 200000, further preferably25000 to 120000, particularly preferably 25000 to 50000.

The Mw of less than 20000 is not preferable since the resin is brittle.The Mw is more than 200000 is not preferable, since the melt viscosityis high, and therefore drawing the resin out of the mold in molding ismade difficult, further the fluidity deteriorates, and handling in amolten state is made difficult.

(2) Production Step (b)

Subsequently, in step (b), an additive is mixed into resin (A) obtainedin step (a) to obtain a resin composition. The mixing temperature T2 instep (b) falls within the range of 250° C.≤T2≤280° C. The mixingtemperature T2 is preferably about 260° C. and is preferably within therange, for example, of 255° C.≤T2≤275° C., 255° C.≤T2≤270° C., 255°C.≤T2≤265° C., or 257° C.≤T2≤263° C.

The method for mixing the additive with resin (A) is not specificallylimited, but pelletization is preferably performed while performing themixing, for example, by using an extruder. In this case, the mixingtemperature T2 in the present invention is a temperature inside theextruder. Even in the case of not using the extruder, the environment inwhich the additive is mixed into resin (A) needs only to fall within therange of the mixing temperature T2. The aforementioned deactivator maybe added together with the additive.

Examples of the additive include antioxidants, processing stabilizers,light stabilizers, heavy metal deactivators, flame retardants,lubricants, antistatic agents, surfactants, antibacterial agents,release agents, ultraviolet absorbers, plasticizers, andcompatibilizers, and an antioxidant and a release agent, for example,are preferably added.

Examples of the antioxidants include triethyleneglycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate],1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate],pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide),3,5-di-tert-butyl-4-hydroxy-benzyl phosphonate-diethyl ester,tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, and3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane,pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.The content of the antioxidants in the resin composition is preferably0.001 to 0.3 parts by weight per 100 parts by weight of the resincomposition.

Examples of the processing stabilizers include phosphorus-basedprocessing heat stabilizers and sulfur-based processing heatstabilizers. Examples of the phosphorus-based processing heatstabilizers include phosphorous acid, phosphoric acid, phosphonous acid,and phosphonic acid, and esters thereof. Specific examples thereofinclude triphenyl phosphite, tris(nonylphenyl) phosphite,tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecylphosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite,diisopropylmonophenyl phosphite, monobutyldiphenyl phosphite,monodecyldiphenyl phosphite, monooctyldiphenyl phosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite,bis(nonylphenyl)pentaerythritol diphosphite,bis(2,4-dicumylphenyl)pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate,trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenylphosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate,dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropylbenzenephosphonate,tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylenediphosphonite,tetrakis(2,4-di-t-butylphenyl)-4,3′-biphenylenediphosphonite,tetrakis(2,4-di-t-butylphenyl)-3,3′-biphenylenediphosphonite,bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, andbis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. The content ofthe phosphorus-based processing heat stabilizers in the resincomposition is preferably 0.001 to 0.2 parts by weight per 100 parts byweight of the resin composition.

Examples of the sulfur-based processing heat stabilizers includepentaerythritol-tetrakis(3-laurylthiopropionate),pentaerythritol-tetrakis(3-myristylthiopropionate),pentaerythritol-tetrakis(3-stearylthiopropionate),dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, anddistearyl-3,3′-thiodipropionate. The content of the sulfur-basedprocessing heat stabilizers in the resin composition is preferably 0.001to 0.2 parts by weight per 100 parts by weight of the resin composition.

As the release agents, release agents with 90 wt % or more consisting ofesters of alcohols and fatty acids are preferable. Specific examples ofthe esters of alcohols and fatty acids include esters of monohydricalcohols and fatty acids, and partial esters or all esters of polyhydricalcohols and fatty acids. As the esters of monohydric alcohols and fattyacids above, esters of monohydric alcohols having 1 to 20 carbon atomsand saturated fatty acids having 10 to 30 carbon atoms are preferable.Further, as the partial esters or all esters of polyhydric alcohols andfatty acids, partial esters or all esters of polyhydric alcohols having1 to 25 carbon atoms and saturated fatty acids having 10 to 30 carbonatoms are preferable.

Specific examples of the esters of monohydric alcohols and saturatedfatty acids include stearyl stearate, palmityl palmitate, butylstearate, methyl laurate, and isopropyl palmitate. Examples of thepartial ester or all esters of polyhydric alcohols and saturated fattyacids include all esters or partial esters of stearic acidmonoglyceride, stearic acid diglyceride, stearic acid triglyceride,stearic acid monosorbitate, behenic acid monoglyceride, capric acidmonoglyceride, lauric acid monoglyceride, pentaerythritol monostearate,pentaerythritol tetrastearate, pentaerythritol tetrapelargonate,propylene glycol monostearate, biphenyl biphenate, sorbitanmonostearate, 2-ethylhexyl stearate, and dipentaerythritol such asdipentaerythritol hexastearate. Among these, stearic acid monoglycerideand lauric acid monoglyceride are particularly preferable. The contentof these release agents is preferably in the range of 0.005 to 2.0 partsby weight, more preferably in the range of 0.01 to 0.6 parts by weight,further preferably in the range of 0.02 to 0.5 parts by weight, per 100parts by weight of the resin composition.

As the ultraviolet absorbers, at least one ultraviolet absorber selectedfrom the group consisting of benzotriazole-based ultraviolet absorbers,benzophenone-based ultraviolet absorbers, triazine-based ultravioletabsorbers, cyclic imino ester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers is preferable. That is, any one ofthe following ultraviolet absorbers may be used alone, or two or more ofthem may be used in combination.

Examples of the benzotriazole-based ultraviolet absorbers include2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)benzotriazole,2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole,2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol],2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole,2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2-hydroxy-3,5-di-tert-amaylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)benzotriazole,2-(2-hydroxy-5-tert-butylphenyl)benzotriazole,2-(2-hydroxy-4-octoxyphenyl)benzotriazole,2.2′-methylenebis(4-cumyl-6-benzotriazole phenyl),2,2′-p-phenylenebis(1,3-benzoxazin-4-one), and2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole.

Examples of the benzophenone-based ultraviolet absorbers include2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone,2-hydroxy-4-methoxy-5-sulfoxybenzophenone,2-hydroxy-4-methoxy-5-sulfoxytrihydratebenzophenone,2,2′-dihydroxy-4-methoxybenzophenone,2,2′,4,4′-tetrahydroxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxy-5-sodium sulfoxybenzophenone,bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane,2-hydroxy-4-n-dodecyloxybenzophenone, and2-hydroxy-4-methoxy-2′-carboxybenzophenone.

Examples of the triazine-based ultraviolet absorbers include2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol,2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-[(octyl)oxy]-phenol,and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Examples of the cyclic imino ester-based ultraviolet absorbers include2,2′-bis(3,1-benzoxazin-4-one),2,2′-p-phenylenebis(3,1-benzoxazin-4-one),2,2′-m-phenylenebis(3,1-benzoxazin-4-one),2,2′-(4,4′-diphenylene)bis(3,1-benzoxazin-4-one),2,2′-(2,6-naphthalene)bis(3,1-benzoxazin-4-one),2,2′-(1,5-naphthalene)bis(3,1-benzoxazin-4-one),2,2′-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one),2,2′-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one), and2,2′-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one).

Examples of the cyano acrylate-based ultraviolet absorbers include1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane,and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

The content of the ultraviolet absorbers is preferably 0.01 to 3.0 partsby weight, more preferably 0.02 to 1.0 part by weight, furtherpreferably 0.05 to 0.8 parts by weight, per 100 parts by weight of theresin composition. When the amount blended falls within theaforementioned range, sufficient weather resistance can be imparted tothe resin depending on the application.

Further, the resin composition of the present invention may containother resins in a range not impairing the properties of the presentinvention, in addition to the resin (A).

Examples of the other resins include: polyethylene, polypropylene,polyvinyl chloride, polystyrene, (meth)acrylic resin, ABS resin,polyamide, polyacetal, polycarbonate, polyphenylene ether, polyester,polyphenylene sulfide, polyimide, polyether sulfone, polyether etherketone, fluororesin, cycloolefin polymer, ethylene-vinyl acetatecopolymer, epoxy resin, silicone resin, phenolic resin, unsaturatedpolyester resin, and polyurethane.

The content of the other resins is preferably 20 parts by mass or less,further preferably 10 parts by mass or less, per 100 parts by weight ofthe resin (A).

When the content of the other resins is excessively high, thetransparency of the resin composition may be reduced due todeterioration in compatibility in some cases. In order to keep a lowoptical strain, the other resins are preferably not contained.

3. Properties of Resin Composition

The resin composition obtained by the method of the present inventionhas small contents of polymers and compounds containing terminal vinylgroups. Specifically, the amount of fluorene-based vinyl terminal groupscalculated by the method described in Examples below is preferably 0.5or less (for example, 0.01 to 0.5, or 0.03 to 0.5), more preferably 0.3or less (for example, 0.03 to 0.3), particularly preferably 0.2 or less(for example, 0.03 to 0.2). Further, the amount of binaphthol-basedvinyl terminal groups is preferably 1.0 or less (for example, 0.05 to1.0, or 0.3 to 1.0), more preferably 0.9 or less (for example, 0.3 to0.9), particularly preferably 0.5 or less (for example, 0.3 to 0.5).

Further, the resin composition obtained by the method of the presentinvention has a small content of compounds containing aliphatic terminalOH groups as well. Specifically, the amount of aliphatic terminal OHgroups calculated by the method described in Examples below ispreferably 0.45 or less (for example, 0.1 to 0.45), more preferably 0.3or less (for example, 0.1 to 0.3), particularly preferably 0.2 or less(for example, 0.1 to 0.2).

Further, the yellowness of the resin composition obtained by the methodof the present invention is preferably less than 20, more preferably 15or less, particularly preferably 13 or less, most preferably 10 or less.

4. Optical Molded Products

Optical molded products can be produced using the resin composition ofthe present invention. The resin composition of the present inventionhas less coloration and therefore can be used advantageously as amaterial for transparent conductive substrates used for liquid crystaldisplays, organic EL displays, solar cells and the like, and opticalmolded products such as optical disks, liquid crystal panels, opticallenses, optical sheets, optical films, optical fibers, connectors, anddeposited plastic reflectors. Such optical molded products containingthe resin composition of the present invention have both high refractiveindex and excellent shapability.

Generally, resins produced using transesterification have branchedstructures in their molecular chains and therefore have high viscosityin the low shear rate region and non-Newtonian properties. Therefore, inthe case of molding such a resin in the low shear region, non-uniformresidual strain tends to occur conventionally, and there have beenproblems of warpage immediately after processing and deformation underhigh-temperature condition. Further, although the fluidity of the resinis improved as the temperature at which the resin is softened increases,the decomposition or coloration of the resin tend to occur duringmolding, and therefore the softening temperature has been constrained.However, the resin composition of the present invention is less likelyto be colored and therefore can solve the problem of coloration that canoccur during molding, while maintaining the fluidity of the resin.Further, molded products to be obtained have both high refractive indexand excellent shapability, and are also excellent in various propertiesthat are desired as optical molded products such as haze, total lighttransmittance, and Abbe number.

The optical molded products are molded by any method such as injectionmolding, compression molding, extrusion, and solution casting. In themolding, the resin composition of the present invention can be used bymixing with another resin such as polycarbonate resins and polyesterresins. Further, additives such as antioxidants, processing stabilizers,light stabilizers, heavy metal deactivators, flame retardants,lubricants, antistatic agents, surfactants, antibacterial agents,release agents, ultraviolet absorbers, plasticizers, and compatibilizersmay be mixed. The detail of such an additive is as described above forthe additive in production step (b).

On a surface of such an optical molded product, a coating layer such asan antireflection layer or a hard coating layer may be provided, asneeded. The antireflection layer may be composed of a single layer ormultiple layers and may be organic matter or inorganic matter but ispreferably inorganic matter. Specific examples thereof include oxides orfluorides such as silicon oxide, aluminum oxide, zirconium oxide,titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

(Optical Films or Optical Sheets)

As an example of the optical molded products, optical films or opticalsheets will be described. Films or sheets containing the resincomposition of the present invention are suitably used, for example, forliquid crystal substrate films, prism sheets for improving thebrightness of liquid crystal display devices, optical memory cards, orthe like.

The structures of the sheets and the films are not specifically limitedand may be a single layer structure or a multilayer structure. In thecase of the multilayer structure, a structure in which two layers, threelayers, or four or more layers composed of different resins arelaminated may be employed.

As a method for producing a sheet and a film, various film formingmethods such as melt extrusion (for example, T-die molding), castcoating (for example, flow casting), calendering, and hot pressing canbe used and is not specifically limited. Preferable examples includemelt extrusion. In the case of using melt extrusion, a well-known meltextrusion machine may be used as an apparatus. Hereinafter, a method forproducing a sheet and a film using melt extrusion will be described.

First, the materials are put into the extruder to be melt-kneaded, andmolten materials in the form of a sheet are extruded from the tip (lip)of a T-die. Examples of the extruder include single-screw extruders andtwin-screw extruders. Further, in the case of producing a multilayerfilm composed of two or more layers, a plurality of extruders may beused. For example, in the case of producing a three-layered film, aftermaterials are respectively melt-kneaded using three or two extruders,the molten materials can be distributed using a three-type three-layerdistribution or two-type three-layer distribution feed block, so as tobe coextruded by flowing into a single layer T-die. Alternatively, themolten materials of the each layer may be allowed to flow into amulti-manifold die and distributed into three layers before the lip, soas to be coextruded.

The extruder may be appropriately provided, for example, with a screenmesh for filtering and removing comparatively large foreign matter, orthe like, in the materials, a polymer filter for filtering and removingcomparatively small foreign matter, gel, or the like, in the materials,and a gear pump for quantifying the amount of resin to be extruded.

The T-die is a die having a slit-shaped lip, and examples thereofinclude feed block dies, manifold dies, fishtail dies, coat hanger dies,and screw dies. In the case of producing a multilayer thermoplasticresin film, multi manifold dies or the like may be used.

Further, the length of the lip in the width direction of the T-die isnot particularly limited but is preferably 1.2 to 1.5 times the width ofthe product. The degree of opening of the lip may be appropriatelyadjusted depending on the thickness of the desired product but isgenerally 1.01 to 10 times, preferably 1.1 to 5 times, the thickness ofthe desired product. The degree of opening of the lip is preferablyadjusted by bolts that are aligned in the width direction of the T-die.The degree of opening of the lip may be non-constant in the widthdirection, and the draw resonance phenomenon can be suppressed, forexample, by adjusting the degree of opening of the lip at the ends to benarrower than the degree of opening of the lip at the center.

Subsequently, the extruded materials in the form of a sheet aresandwiched between two cooling rolls to be molded. The two cooling rollsboth may be metal rolls or elastic rolls, or one of them may be a metalroll, with the other being an elastic roll. The surface state of therolls is not specifically limited and may be mirror surfaces or may havepatterns or projections and recesses, for example.

The metal rolls are not specifically limited as long as they have highstiffness, and examples thereof include drilled rolls and spiral rolls.

Examples of the elastic rolls include rubber rolls and elastic rollsprovided with metal thin films on their outer circumferences(hereinafter also referred to as metal elastic rolls). Among these,metal elastic rolls are preferable.

The gap between the two cooling rolls (roll gap) is appropriatelyadjusted depending on the thickness of the desired product, and the rollgap is set so that both surfaces of the materials in the form of a sheetare respectively in contact with the surfaces at the center of thecooling rolls. Therefore, upon being sandwiched by the two coolingrolls, the materials in the form of a sheet are subjected to a constantpressure from the center of the cooling rolls, to be formed into a filmor a sheet.

The crimping pressure of the two cooling rolls is arbitrary within theallowable range of the stiffness of the rolls. Further, the formingspeed into a sheet and a film also can be appropriately adjusted.

In order to avoid contamination of foreign matter into the film as muchas possible, the forming environment of course needs to be a low dustenvironment and is preferably class 6 or lower, more preferably class 5or lower.

(Optical Lenses)

Specific examples of the optical molded products also include opticallenses. Optical lenses containing the resin composition of the presentinvention can be used in the fields in which expensive glass lenses withhigh refractive index have been conventionally used such as telescopes,binoculars, and television projectors, and are exceptionally useful.Using in the form of an aspherical lens, as needed, is preferable. Theaspherical lens can reduce the spherical aberration to substantiallyzero even with one aspherical lens, and therefore there is no need toeliminate the spherical aberration by combining a plurality of sphericallenses, thereby enabling a reduction in weight and a reduction inproduction cost. Accordingly, the aspherical lens is particularly usefulas a camera lens among optical lenses.

The optical lens is molded by any method such as injection molding,compression molding, and injection compression molding. Asphericallenses with high refractive index and low birefringence, processing ofwhich is technically difficult by using glass lenses, can beconveniently obtained by using the resin composition of the presentinvention.

Since the resin composition of the present invention has high fluidity,optical lenses having complex shapes with reduced thickness and reducedsize can be produced. As a specific lens size, the thickness in thecenter portion is 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm,further preferably 0.1 to 2.0 mm. Further, the diameter is 1.0 mm to20.0 mm, more preferably 1.0 to 10.0 mm, further preferably 3.0 to 10.0mm.

In order to avoid contamination of foreign matter into the optical lensas much as possible, the molding environment of course needs to be a lowdust environment and is preferably class 6 or lower, more preferablyclass 5 or lower.

EXAMPLES

Hereinafter, the present invention will be described by way of examples,but the present invention is not limited to these examples at all.

1. Resin Composition

The melt volume rate (MVR) and the yellowness in Examples were measuredusing the following methods.

(1) Melt volume rate (MVR)

The MVR is an index indicating the fluidity of the resin composition,and a larger value indicates a higher fluidity. Resins produced inExamples and Comparative Examples were dried at 120° C. under vacuum for4 hours and were measured, using a melt indexer T-111 manufactured byToyo Seiki Seisaku-sho, Ltd., under conditions of a temperature of 260°C. and a load of 2160 g.

(2) Yellowness

The resins produced in Examples and Comparative Examples were subjectedto vacuum drying at 120° C. for 4 hours, followed by injection molding,to obtain test pieces (having a disk shape) with a diameter of 50 mm anda thickness of 3 mm. The yellowness was measured using these testpieces. For the measurement, a double beam spectrophotometer U-2910,manufactured by Hitachi High-Tech Science Corporation, was used.

Further, ¹H-NMR measurement conditions were as follows.

-   (3) ¹H-NMR Measurement Conditions-   Apparatus: AVANCE III HD 500 MHz, manufactured by Bruker Corporation-   Flip angle: 30 degrees-   Waiting time: 1 second-   Cumulative number of times: 500 times-   Measurement temperature: Room temperature (298K)-   Concentration: 5 wt %-   Solvent: Deuterated chloroform-   Internal standard substance: Tetramethylsilane (TMS) 0.05 wt %

Example 1 BPEF homopolymer, T1=240° C., T2=260° C.

17.99 kg (41.01 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene(hereinafter also referred to as “BPEEF”), 9.14 kg (42.65 mol) ofdiphenyl carbonate (hereinafter also referred to as “DPC”), and2.07×10⁻² g (2.46×10⁻⁴ mol) of sodium hydrogen carbonate were put into a50-liter reactor equipped with a stirrer and a distillation apparatus.After conducting nitrogen purging, the mixture was stirred while beingheated to 205° C. over 1 hour in a nitrogen atmosphere of 760 Torr.After the complete dissolution of the raw materials, the pressurereduction degree was adjusted to 150 Torr over 15 minutes, and themixture was held for 20 minutes under conditions of 205° C. and 150Torr, followed by transesterification reaction. Further, the temperaturewas raised to 240° C. at a rate of 37.5° C./hr, and the mixture was heldat 240° C. and 150 Torr for 10 minutes. Thereafter, the pressure wasadjusted to 120 Torr over 10 minutes, and the mixture was held at 240°C. and 120 Torr for 70 minutes. Thereafter, the pressure was adjusted to100 Torr over 10 minutes, and the mixture was held at 240° C. and 100Torr for 10 minutes. Further, the pressure was reduced to 1 Torr or lessover 40 minutes, and polymerization reaction was performed understirring for 10 minutes under conditions of 240° C. and 1 Torr or less.After the completion of the reaction, nitrogen was blown into thereactor for pressurization, and the produced polycarbonate resin wastaken out while being pelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 260° C.

The MVR of the resin composition obtained was 30 cm³/min, the yellownesswas 5, the amount of aliphatic terminal OH groups was 0.103, and theamount of fluorene-based vinyl terminal groups was 0.198. The amount ofaliphatic terminal OH groups and the amount of fluorene-based vinylterminal groups were calculated by the methods described below.

Comparative Example 1 BPEF homopolymer, T1=265° C., T2=285° C.

The same amounts of BPEF, DPC, and sodium hydrogen carbonate as inExample 1 were put into a 50-liter reactor equipped with a stirrer and adistillation apparatus. After conducting nitrogen purging, the mixturewas stirred under heating to 205° C. over 1 hour in a nitrogenatmosphere of 760 Torr. After the complete dissolution of the rawmaterials, the pressure reduction degree was adjusted to 150 Torr over15 minutes, and the mixture was held for 20 minutes under conditions of205° C. and 150 Torr, followed by transesterification reaction.Thereafter, the temperature was raised to 265° C. at a rate of 37.5°C./hr, and the mixture was held at 265° C. and 150 Torr for 10 minutes.Thereafter, the pressure was adjusted to 120 Torr over 10 minutes, andthe mixture was held at 265° C. and 120 Torr for 70 minutes. Thereafter,the pressure was adjusted to 100 Torr over 10 minutes, and the mixturewas held at 265° C. and 100 Torr for 10 minutes. Further, the conditionswere changed to 1 Torr or less over 40 minutes, and polymerizationreaction was performed under stirring for 10 minutes under conditions of265° C. and 1 Torr or less. After the completion of the reaction,nitrogen was blown into the reactor for pressurization, and the producedpolycarbonate resin was taken out while being pelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 285° C.

The MVR of the resin composition obtained was 30 cm³/min, the yellownesswas 20, the amount of aliphatic terminal OH groups was 0.070, and theamount of fluorene-based vinyl terminal groups was 0.510. The amount ofaliphatic terminal OH groups and the amount of fluorene-based vinylterminal groups were calculated in the same manner as in Example 1.

Comparative Example 2 BPEF homopolymer; T1=230° C., T2=245° C.

The same amounts of BPEF, DPC, and sodium hydrogen carbonate as inExample 1 were put into a 50-liter reactor equipped with a stirrer and adistillation apparatus. After conducting nitrogen purging, the mixturewas stirred under heating to 205° C. over 1 hour in a nitrogenatmosphere of 760 Torr. After the complete dissolution of the rawmaterials, the pressure reduction degree was adjusted to 150 Torr over15 minutes, and the mixture was held for 20 minutes under conditions of205° C. and 150 Torr, followed by transesterification reaction.Thereafter, the temperature was raised to 230° C. at a rate of 37.5°C./hr, and the mixture was held at 230° C. and 150 Torr for 10 minutes.Thereafter, the pressure was adjusted to 120 Torr over 10 minutes, andthe mixture was held at 230° C. and 120 Torr for 70 minutes. Thereafter,the pressure was adjusted to 100 Torr over 10 minutes, and the mixturewas held at 230° C. and 100 Tort for 10 minutes. Further, the conditionswere changed to 1 Torr or less over 40 minutes, and polymerizationreaction was performed under stirring for 10 minutes under conditions of230° C. and 1 Torr or less. After the completion of the reaction,nitrogen was blown into the reactor for pressurization, and the producedpolycarbonate resin was taken out while being pelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 245° C.

The MVR of the resin composition obtained was 35 cm³/min, the yellownesswas 21, the amount of aliphatic terminal OH groups was 0.463, and theamount of fluorene-based vinyl terminal groups was 0.550. The amount ofaliphatic terminal OH groups and the amount of fluorene-based vinylterminal groups were calculated in the same manner as in Example 1.

(Method for Calculating Amount of Fluorene-Based Vinyl Terminal Groups)

The polycarbonate resins obtained in Example 1 and Comparative Examples1 and 2 contain the following repeating unit.

wherein Ha represents a hydrogen atom.

Further, a polymer and/or a compound described below is contained in theresin compositions as a by-product generated by polymerization reaction:

wherein * represents a polymer chain, and He represents a hydrogen atom.

Here, vinyl groups located at the terminals of formulas (A) and (B) arereferred to as “fluorene-based vinyl terminal groups.” The ¹H-NMRspectrum of the resin compositions obtained in Example 1 and ComparativeExamples 1 and 2 was measured, and the amount of fluorene-based vinylterminal groups was calculated using the following expression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{fluorene}\text{-}{based}\mspace{14mu}{vinyl}\mspace{14mu}{terminal}\mspace{14mu}{groups}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hc}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Ha}} \times 100}$

In the aforementioned expression, it can be considered as:

$\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hc}}{{Integral}\mspace{14mu}{value}\mspace{20mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Ha}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.75\mspace{14mu}{to}\mspace{14mu} 4.69\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 7.83\mspace{14mu}{to}\mspace{14mu} 7.65\mspace{14mu}{ppm}}.}$(Method for Calculating Amount of Aliphatic Terminal OH Groups)

The resin compositions obtained in Example 1 and Comparative Examples 1and 2 contain a polymer as described below in which a structure having ahydroxyalkyl group is located at a terminal as an unreacted compound ora by-product:

wherein * represents a polymer chain.

Here, the terminal OH group bound to an alkylene group as shown informula (C) is referred to as “aliphatic terminal OH group”. Based onthe ¹H-NMR spectra of the resin compositions obtained in Example 1 andComparative Examples 1 and 2, the amount of aliphatic terminal OH groupswas calculated using the following expression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{aliphatic}\mspace{14mu}{terminal}\mspace{14mu}{OH}\mspace{14mu}{groups}} = {\frac{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{hydroxyl}} \\{{groups}\mspace{14mu}{in}\mspace{14mu}{compound}\mspace{14mu}{of}\mspace{14mu}{formula}\mspace{11mu}(C)}\end{matrix}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{{Ha}/2}} \times 100.}$In the aforementioned formula, it can be considered as:

$\frac{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{hydroxyl}} \\{{groups}\mspace{14mu}{in}\mspace{14mu}{compound}\mspace{14mu}{of}\mspace{14mu}{formula}\mspace{11mu}(C)}\end{matrix}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Ha}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 2.02\mspace{14mu}{to}\mspace{14mu} 1.95\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 7.83\mspace{14mu}{to}\mspace{14mu} 7.65\mspace{14mu}{ppm}}.}$

¹H-NMR chart of the resin composition produced in Example 1 is shown inFIG. 1(a). FIGS. 1(b) and (c) are enlarged partial views of FIG. 1(a).The ¹H-NMR chart of the resin composition produced in ComparativeExample 1 is shown in FIG. 5(a). FIG. 5(b) is an enlarged partial viewof FIG. 5(a). The ¹H-NMR chart of the resin composition produced inComparative Example 2 is shown in FIG. 6(a). FIG. 6(b) is an enlargedpartial view of FIG. 6(a).

Example 2 Copolymer of BPEF and BHEBN; T1=240° C., T2=260° C.

7.80 kg (20.83 mol) of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthyl(hereinafter also referred to as “BHEBN”), 12.56 kg (28.65 mol) of BPEF,10.90 kg (50.87 mol) of DPC, and 2.49×10⁻² g (2.97×10⁻⁴ mol) of sodiumhydrogen carbonate were put into a 50-liter reactor equipped with astirrer and a distillation apparatus. After conducting nitrogen purging,the temperature was raised to 205° C. over 20 minutes in a nitrogenatmosphere of 760 Torr. Thereafter, the raw materials were melted whilethe pressure was reduced to 700 Torr over 10 minutes. The mixture washeld for 10 minutes as it was, followed by stirring, and was furtherheld for 100 minutes, and thereafter the pressure was reduced to 205Torr over 20 minutes. After the mixture was held for 60 minutes as itwas, the pressure was adjusted to 180 Torr over 10 minutes, and themixture was held for 20 minutes under conditions of 215° C. and 180Torr. The pressure was adjusted to 150 Torr further over 10 minutes, andthe mixture was held for 30 minutes under conditions of 230° C. and 150Torr. Thereafter, the pressure was reduced to 120 Torr, and thetemperature was raised to 240° C. Thereafter, the pressure was reducedto 100 Torr over 10 minutes, and the mixture was held for 10 minutes.The pressure was reduced to 1 Torr or less further over 50 minutes, andthe mixture was held for 40 minutes under conditions of 240° C. and 1Torr or less. After the completion of the reaction, nitrogen was blowninto the reactor for pressurization, and the produced polycarbonateresin was taken out while being pelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 260° C.

The MVR of the obtained resin composition was 32 cm³/min, the yellownesswas 15, the amount of aliphatic terminal OH groups was 0.425, the amountof fluorene-based vinyl terminal groups was 0.030, and the amount ofbinaphthol-based vinyl terminal groups was 0.443. The amount ofaliphatic terminal OH groups, the amount of fluorene-based vinylterminal groups, and the amount of binaphthol-based vinyl terminalgroups were calculated by the methods described below.

Example 2-1 Copolymer of BPEF and BHEBN; T1=235° C., T2=255° C.

The raw materials were put into a 50-liter reactor equipped with astirrer and a distillation apparatus in the same manner as in Example 2.After conducting nitrogen purging, the temperature was raised to 205° C.over 20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, theraw materials were melted while the pressure was reduced to 700 Torrover 10 minutes. The mixture was held for 10 minutes as it was, followedby stirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 235° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 235° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 255° C. Thephysical properties of the obtained polycarbonate composition are shownin Table 1.

Example 2-2 Copolymer of BPEF and BHEBN; T1=245° C., T2=270° C.

The raw materials were put into a 50-liter reactor equipped with astirrer and a distillation apparatus in the same manner as in Example 2.After conducting nitrogen purging, the temperature was raised to 205° C.over 20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, theraw materials were melted while the pressure was reduced to 700 Torrover 10 minutes. The mixture was held for 10 minutes as it was, followedby stirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 245° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 245° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 270° C. Thephysical properties of the obtained polycarbonate composition are shownin Table 1.

Comparative Example 2-1 Copolymer of BPEF and BHEBN; T1=240° C., T2=290°C.

The raw materials were put into a 50-liter reactor equipped with astirrer and a distillation apparatus in the same manner as in Example 2.After conducting nitrogen purging, the temperature was raised to 205° C.over 20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, theraw materials were melted while the pressure was reduced to 700 Torrover 10 minutes. The mixture was held for 10 minutes as it was, followedby stirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 240° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 240° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 290° C. Thephysical properties of the obtained polycarbonate composition are shownin Table 1.

Comparative Example 2-2 Copolymer of BPEF and BHEBN; T1=270° C., T2=270°C.

The raw materials were put into a 50-liter reactor equipped with astirrer and a distillation apparatus in the same manner as in Example 2.After conducting nitrogen purging, the temperature was raised to 205° C.over 20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, theraw materials were melted while the pressure was reduced to 700 Torrover 10 minutes. The mixture was held for 10 minutes as it was, followedby stirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 270° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 270° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 270° C. Thephysical properties of the obtained polycarbonate composition are shownin Table 1.

(Method for Calculating Amount of Fluorene-Based Vinyl Terminal Groups)

The polycarbonate resins obtained in Examples 2, 2-1 and 2-2 andComparative Examples 2-1 and 2-2 contain the following repeating units.

wherein Hm and Hk each represent a hydrogen atom.

Further, a polymer and/or a compound described below is contained in theresin compositions as a by-product generated by polymerization reaction.

wherein * represents a polymer chain, and He represents a hydrogen atom.

Here, vinyl groups located at the terminals of formulas (A) and (B) arereferred to as “fluorene-based vinyl terminal groups.” The ¹H-NMRspectrum of the resin compositions obtained in Examples 2, 2-1 and 2-2and Comparative Examples 2-1 and 2-2 was measured, and the amount offluorene-based vinyl terminal groups was calculated using the followingexpression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{fluorene}\text{-}{based}\mspace{14mu}{vinyl}\mspace{14mu}{terminal}\mspace{14mu}{groups}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hc}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hm}\mspace{14mu}{and}\mspace{14mu}{Hk}} \times 100.}$

In the aforementioned expression, it can be considered as:

$\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hc}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hm}\mspace{14mu}{and}\mspace{14mu}{Hk}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.75\mspace{14mu}{to}\mspace{14mu} 4.69\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}}.}$(Method for Calculating Amount of Binaphthol-Based Vinyl TerminalGroups)

The resin compositions obtained in Examples 2, 2-1 and 2-2 andComparative Examples 2-1 and 2-2 also contain a polymer and/or acompound described below, other than the components described above in“Method for calculating amount of fluorene-based vinyl terminal groups”.

wherein * represents a polymer chain, and Hp represents a hydrogen atom.

Here, vinyl groups located at the terminals of formulas (D) and (E) arereferred to as “binaphthol-based vinyl terminal groups.” Based on the¹H-NMR spectrum of the resin compositions obtained in Examples 2, 2-1and 2-2 and Comparative Examples 2-1 and 2-2, the amount ofbinaphthol-based vinyl terminal groups was calculated using thefollowing expression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{binaphthol}\text{-}{based}\mspace{14mu}{vinyl}\mspace{14mu}{terminal}\mspace{14mu}{groups}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hp}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hm}\mspace{14mu}{and}\mspace{14mu}{Hk}} \times 100.}$

In the aforementioned expression, it can be considered as:

$\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hp}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hm}\mspace{14mu}{and}\mspace{14mu}{Hk}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.69\mspace{14mu}{to}\mspace{14mu} 4.59\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}}.}$(Method for Calculating Amount of Aliphatic Terminal OH Groups)

The resin compositions obtained in Examples 2, 2-1, and 2-2 andComparative Examples 2-1 and 2-2 contain a polymer as described below inwhich a structure having a hydroxyalkyl group is located at a terminalas an unreacted compound or a by-product:

wherein * represents a polymer chain.

Here, terminal OH groups bound to alkylene groups as shown in formulas(C) and (F) are referred to as “aliphatic terminal OH groups”. Based onthe ¹H-NMR spectra of the resin compositions obtained in Examples 2,2-1, and 2-2, and Comparative Examples 2-1 and 2-2, the amount ofaliphatic terminal OH groups was calculated using the followingexpression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{aliphatic}\mspace{14mu}{terminal}\mspace{14mu}{OH}\mspace{14mu}{groups}} = {\frac{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{hydroxyl}} \\{{groups}\mspace{14mu}{in}\mspace{14mu}{compounds}\mspace{14mu}{of}\mspace{14mu}{formulas}\mspace{11mu}(C)\mspace{14mu}{and}\mspace{14mu}(F)}\end{matrix}}{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}} \\{{Hm}\mspace{14mu}{and}\mspace{14mu}{{Hk}/8}}\end{matrix}\mspace{14mu}} \times 100.}$

In the aforementioned formula, it can be considered as:

$\frac{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{hydroxyl}} \\{{groups}\mspace{14mu}{in}\mspace{14mu}{compounds}\mspace{14mu}{of}\mspace{14mu}{formulas}\mspace{11mu}(C)\mspace{14mu}{and}\mspace{14mu}(F)}\end{matrix}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hm}\mspace{14mu}{and}\mspace{14mu}{Hk}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 2.02\mspace{14mu}{to}\mspace{14mu} 1.95\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}}.}$

¹H-NMR chart of a resin composition produced in Example 2 is shown inFIG. 2(a). FIG. 2(b) is an enlarged partial view of FIG. 2(a).

Example 3 Copolymer of BPPEF and BHEBN; T1=240° C., T2=260° C.

7.43 kg (19.83 mol) of BHEBN, 14.69 kg (24.87 mol) of9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (hereinafter alsoreferred to as “BPPEF”), 9.70 kg (45.29 mol) of DPC, and 2.41×10⁻² g(2.86×10⁻⁴ mol) of sodium hydrogen carbonate were put into a 50-literreactor equipped with a stirrer and a distillation apparatus. Afterconducting nitrogen purging, the temperature was raised to 205° C. over20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, the rawmaterials were melted while the pressure was reduced to 700 Torr over 10minutes. The mixture was held for 10 minutes as it was, followed bystirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 240° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 240° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 260° C.

The MVR of the obtained resin composition was 32 cm³/min, the yellownesswas 13, the amount of aliphatic terminal OH groups was 0.102, the amountof fluorene-based vinyl terminal groups was 0.036, and the amount ofbinaphthol-based vinyl terminal groups was 0.416. The amount ofaliphatic terminal OH groups, the amount of fluorene-based vinylterminal groups, and the amount of binaphthol-based vinyl terminalgroups were calculated by the methods described below.

Example 3-1 Copolymer of BPPEF and BHEBN; T1=235° C., 12=255° C.

7.43 kg (19.83 mol) of BHEBN, 14.69 kg (24.87 mol) of9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (hereinafter alsoreferred to as “BPPEF”), 9.70 kg (45.29 mol) of DPC, and 2.41×10⁻² g(2.86×10⁻⁴ mol) of sodium hydrogen carbonate were put into a 50-literreactor equipped with a stirrer and a distillation apparatus. Afterconducting nitrogen purging, the temperature was raised to 205° C. over20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, the rawmaterials were melted while the pressure was reduced to 700 Torr over 10minutes. The mixture was held for 10 minutes as it was, followed bystirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 235° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 235° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 255° C. Thephysical properties of the obtained polycarbonate composition are shownin Table 1.

Example 3-2 Copolymer of BPPEF and BHEBN; T1=245° C., T2=270° C.

7.43 kg (19.83 mol) of BHEBN, 14.69 kg (24.87 mol) of9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (hereinafter alsoreferred to as “BPPEF”), 9.70 kg (45.29 mol) of DPC, and 2.41×10⁻² g(2.86×10⁻⁴ mol) of sodium hydrogen carbonate were put into a 50-literreactor equipped with a stirrer and a distillation apparatus. Afterconducting nitrogen purging, the temperature was raised to 205° C. over20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, the rawmaterials were melted while the pressure was reduced to 700 Torr over 10minutes. The mixture was held for 10 minutes as it was, followed bystirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 245° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 245° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 270° C. Thephysical properties of the obtained polycarbonate composition are shownin Table 1.

Comparative Example 3-1 Copolymer of BPPEF and BHEBN; T1=240° C.,T2=290° C.

7.43 kg (19.83 mol) of BHEBN, 14.69 kg (24.87 mol) of9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (hereinafter alsoreferred to as “BPPEF”), 9.70 kg (45.29 mol) of DPC, and 2.41×10⁻² g(2.86×10⁻⁴ mol) of sodium hydrogen carbonate were put into a 50-literreactor equipped with a stirrer and a distillation apparatus. Afterconducting nitrogen purging, the temperature was raised to 205° C. over20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, the rawmaterials were melted while the pressure was reduced to 700 Torr over 10minutes. The mixture was held for 10 minutes as it was, followed bystirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 240° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 240° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 290° C. Thephysical properties of the obtained polycarbonate composition are shownin Table 1.

Comparative Example 3-2 Copolymer of BPPEF and BHEBN; T1=270° C.,T2=270° C.

7.43 kg (19.83 mol) of BHEBN, 14.69 kg (24.87 mol) of9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (hereinafter alsoreferred to as “BPPEF”), 9.70 kg (45.29 mol) of DPC, and 2.41×10⁻² g(2.86×10⁻⁴ mol) of sodium hydrogen carbonate were put into a 50-literreactor equipped with a stirrer and a distillation apparatus. Afterconducting nitrogen purging, the temperature was raised to 205° C. over20 minutes in a nitrogen atmosphere of 760 Torr. Thereafter, the rawmaterials were melted while the pressure was reduced to 700 Torr over 10minutes. The mixture was held for 10 minutes as it was, followed bystirring, and was further held for 100 minutes, and thereafter thepressure was reduced to 205 Torr over 20 minutes. After the mixture washeld for 60 minutes as it was, the pressure was adjusted to 180 Torrover 10 minutes, and the mixture was held for 20 minutes underconditions of 215° C. and 180 Torr. The pressure was adjusted to 150Torr further over 10 minutes, and the mixture was held for 30 minutesunder conditions of 230° C. and 150 Torr. Thereafter, the pressure wasreduced to 120 Torr, and the temperature was raised to 270° C.Thereafter, the pressure was reduced to 100 Torr over 10 minutes, andthe mixture was held for 10 minutes. The pressure was reduced to 1 Torror less further over 50 minutes, and the mixture was held for 40 minutesunder conditions of 270° C. and 1 Torr or less. After the completion ofthe reaction, nitrogen was blown into the reactor for pressurization,and the produced polycarbonate resin was taken out while beingpelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 270° C. Thephysical properties of the obtained polycarbonate composition are shownin Table 1.

(Method for Calculating Amount of Fluorene-Based Vinyl Terminal Groups)

The polycarbonate resins obtained in Examples 3, 3-1 and 3-2 andComparative Examples 3-1 and 3-2 contain the following repeating units.

wherein Hg and Hk each represent a hydrogen atom.

Further, a polymer and/or a compound described below is contained in theresin compositions as a by-product generated by polymerization reaction.

wherein * represents a polymer chain, and Hd represents a hydrogen atom.

Here, vinyl groups located at the terminals of formulas (G) and (H) arerefereed to as “fluorene-based vinyl terminal groups.” The ¹H-NMRspectrum of the resin compositions obtained in Examples 3, 3-1 and 3-2and Comparative Examples 3-1 and 3-2 was measured, and the amount offluorene-based vinyl terminal groups was calculated using the followingexpression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{fluorene}\text{-}{based}\mspace{14mu}{vinyl}\mspace{14mu}{terminal}\mspace{14mu}{groups}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hd}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hg}\mspace{14mu}{and}\mspace{14mu}{Hk}} \times 100.}$

In the aforementioned expression, it can be considered as:

$\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hd}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hg}\mspace{14mu}{and}\mspace{14mu}{Hk}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.59\mspace{14mu}{to}\mspace{14mu} 4.55\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}}.}$(Method for Calculating Amount of Binaphthol-Based Vinyl TerminalGroups)

The resin compositions obtained in Examples 3, 3-1 and 3-2 andComparative Examples 3-1 and 3-2 also contain a polymer and/or acompound described below, other than the components described above in“Method for calculating amount of fluorene-based vinyl terminal groups”.

wherein * represents a polymer chain, and Hp represents a hydrogen atom.

Here, vinyl groups located at the terminals of formulas (D) and (E) arereferred to as “binaphthol-based vinyl terminal groups.” Based on the¹H-NMR spectrum of the resin compositions obtained in Examples 3, 3-1and 3-2 and Comparative Examples 3-1 and 3-2, the amount ofbinaphthol-based vinyl terminal groups was calculated using thefollowing expression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{binaphthol}\text{-}{based}\mspace{14mu}{vinyl}\mspace{14mu}{terminal}\mspace{14mu}{groups}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hp}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hg}\mspace{14mu}{and}\mspace{14mu}{Hk}} \times 100.}$

In the aforementioned expression, it can be considered as:

$\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hp}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hg}\mspace{14mu}{and}\mspace{14mu}{Hk}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.69\mspace{14mu}{to}\mspace{14mu} 4.59\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}}.}$(Method for Calculating Amount of Aliphatic Terminal OH Groups)

The resin compositions obtained in Examples 3, 3-1, and 3-2, andComparative Examples 3-1 and 3-2 contain a polymer as described below inwhich a structure having a hydroxyalkyl group is located at a terminalas an unreacted compound or a by-product:

wherein * represents a polymer chain.

Here, terminal OH groups bound to alkylene groups as shown in formulas(I) and (F) are referred to as “aliphatic terminal OH groups”. Based onthe ¹H-NMR spectra of the resin compositions obtained in Examples 3,3-1, and 3-2, and Comparative Examples 3-1 and 3-2, the amount ofaliphatic terminal OH groups was calculated using the followingexpression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{aliphatic}\mspace{14mu}{terminal}\mspace{14mu}{OH}\mspace{14mu}{groups}} = {\frac{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{hydroxyl}} \\{{groups}\mspace{14mu}{in}\mspace{14mu}{compounds}\mspace{14mu}{of}\mspace{14mu}{formulas}\mspace{11mu}(I)\mspace{14mu}{and}\mspace{14mu}(F)}\end{matrix}}{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}} \\{{Hg}\mspace{14mu}{and}\mspace{14mu}{Hk}}\end{matrix}\mspace{14mu}} \times 100.}$

In the aforementioned formula, it can be considered as:

$\frac{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{hydroxyl}} \\{{groups}\mspace{14mu}{in}\mspace{14mu}{compounds}\mspace{14mu}{of}\mspace{14mu}{formulas}\mspace{11mu}(I)\mspace{14mu}{and}\mspace{14mu}(F)}\end{matrix}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Hg}\mspace{14mu}{and}\mspace{14mu}{Hk}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 2.02\mspace{14mu}{to}\mspace{14mu} 1.95\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}}.}$

¹H-NMR chart of the resin composition produced in Example 3 is shown inFIG. 3(a). FIG. 3(b) is an enlarged partial view of FIG. 3(a).

Example 4 Copolymer of BPEF and bisphenol A; T1=240° C., T2=260° C.

16.09 kg (36.69 mol) of BPEF, 13.06 kg (5.72 mol) of2,2-bis(4-hydroxyphenyl)propane (hereinafter also referred to as“bisphenol A”), 9.51 kg (44.39 mol) of DPC, and 2.14×10⁻² g (2.54×10⁻⁴mol) of sodium hydrogen carbonate were put into a 50-liter reactorequipped with a stirrer and a distillation apparatus. After conductingnitrogen purging, the mixture was stirred while being heated to 205° C.over 1 hour in a nitrogen atmosphere of 760 Torr. After the completedissolution of the raw materials, the pressure reduction degree wasadjusted to 150 Torr over 15 minutes, and the mixture was held for 20minutes under conditions of 205° C. and 150 Torr, followed bytransesterification reaction. Thereafter, the temperature was raised to240° C. at a rate of 37.5° C./hr, and the mixture was held at 240° C.and 150 Torr for 10 minutes. Thereafter, the pressure was adjusted to120 Torr over 10 minutes, and the mixture was held at 240° C. and 120Torr for 70 minutes. Thereafter, the pressure was adjusted to 100 Torrover 10 minutes, and the mixture was held at 240° C. and 100 Torr for 10minutes. Further, the conditions were changed to 1 Torr or less over 40minutes, and polymerization reaction was performed under stirring for 10minutes under conditions of 240° C. and 1 Torr or less. After thecompletion of the reaction, nitrogen was blown into the reactor forpressurization, and the produced polycarbonate resin was taken out whilebeing pelletized.

0.02 parts by weight of glycerol monostearate (RIKEMAL S-100A,manufactured by RIKEN VITAMIN Co., Ltd.), 0.1 parts by weight ofpentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADK STAB AO-60, manufactured by ADEKA CORPORATION), and0.03 parts by weight of3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane(ADK STAB PEP-36, manufactured by ADEKA CORPORATION) per 100 parts byweight of polycarbonate resin pellet taken out were compounded using avented twin-screw extruder (IPEC, manufactured by NIIGATA ENGINEERINGCO., LTD.; complete meshing, rotation in the same direction) to obtain apolycarbonate resin composition.

The extrusion conditions were an output rate of 10 kg/h, a screwrotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusiontemperature from the first supply port to the die part of 260° C.

The MVR of the resin composition obtained was 30 cm³/min, the yellownesswas 7, the amount of aliphatic terminal OH groups was 0.209, and theamount of fluorene-based vinyl terminal groups was 0.150. The amount offluorene-based vinyl terminal groups was calculated in the same manneras in Example 1. The amount of aliphatic terminal OH groups wascalculated by the method shown below.

(Method for Calculating Amount of Aliphatic Terminal OH Groups)

The polycarbonate resins obtained in Example 4 contain the followingrepeating unit.

wherein Ha represents a hydrogen atom.

The resin composition obtained in Example 4 contains a polymer asdescribed below in which a structure having a hydroxyalkyl group islocated at a terminal as an unreacted compound or a by-product:

wherein * represents a polymer chain.

Here, terminal OH groups bound to alkylene groups as shown in formula(C) are referred to as “aliphatic terminal OH groups”. Based on the¹H-NMR spectrum of the resin composition obtained in Example 4, theamount of aliphatic terminal OH groups was calculated using thefollowing expression:

${{Amount}\mspace{14mu}{of}\mspace{14mu}{aliphatic}\mspace{14mu}{terminal}\mspace{14mu}{OH}\mspace{14mu}{groups}} = {\frac{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{hydroxyl}} \\{{groups}\mspace{14mu}{in}\mspace{14mu}{compounds}\mspace{14mu}{of}\mspace{14mu}{formula}\mspace{11mu}(C)}\end{matrix}}{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}} \\{{{Ha}/0.87}/2}\end{matrix}\mspace{14mu}} \times 100.}$

In the aforementioned formula, it can be considered as:

$\frac{\begin{matrix}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{hydroxyl}} \\{{groups}\mspace{14mu}{in}\mspace{14mu}{compounds}\mspace{14mu}{of}\mspace{14mu}{formula}\mspace{11mu}(C)}\end{matrix}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{proton}\mspace{14mu}{peaks}\mspace{14mu}{corresponding}\mspace{14mu}{to}\mspace{14mu}{Ha}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 2.02\mspace{14mu}{to}\mspace{14mu} 1.95\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 4.80\mspace{14mu}{to}\mspace{14mu} 2.80\mspace{14mu}{ppm}}.}$

¹H-NMR chart of the resin composition produced in Example 4 is shown inFIG. 4(a). FIG. 4(b) is an enlarged partial view of FIG. 4(a).

Table 1 below summarizes the amount of fluorene-based vinyl terminalgroups and/or the amount of binaphthol-based vinyl terminal groups, andthe amount of aliphatic terminal OH groups calculated in Examples 1 to4, 2-1, 2-2, 3-1, and 3-2, and Comparative Examples 1, 2, 2-1, 2-2, 3-1,and 3-2, and the values of the MVR and the yellowness measured therein.

TABLE 1 Amount of Amount of fluorene- binaphthol- Amount of ReactionExtrusion based vinyl based vinyl aliphatic temperature temperatureterminal terminal terminal T1 T2 MVR groups groups Yellowness OH groups° C. ° C. cm³/10 min % % — % Example 1 240 260 30 0.198 — 5 0.103Comparative 265 285 30 0.510 — 20 0.070 Example 1 Comparative 230 245 350.550 — 21 0.463 Example 2 Example 2 240 260 32 0.030 0.443 15 0.425Example 2-1 235 255 30 0.210 0.321 14 0.221 Example 2-2 245 270 30 0.3020.821 16 0.190 Comparative 240 290 33 0.621 1.100 25 0.520 Example 2-1Comparative 270 270 30 0.520 1.102 23 0.511 Example 2-2 Example 3 240260 32 0.036 0.416 13 0.102 Example 3-1 235 255 30 0.250 0.269 14 0.125Example 3-2 245 270 30 0.400 0.789 15 0.250 Comparative 240 290 33 0.6211.201 25 0.600 Example 3-1 Comparative 270 270 30 0.520 1.330 23 0.502Example 3-2 Example 4 240 260 30 0.150 — 7 0.209

It is understood from Table 1 that, in the resin compositions of thepresent invention, the values of yellowness were low, and coloration wassuppressed. This is probably because the amounts of compounds(by-products) having vinyl terminal groups and compounds havingaliphatic terminal OH groups contained in the resin compositions weresmall.

Generally, in the case where the polymerization temperature and themixing temperature are low, the amount of aliphatic terminal OH groupstends to be large. An increase in amount of OH groups causes adeterioration in hydrolysis resistance, as is generally known. When thehydrolysis resistance deteriorates, the amount of decomposed productsproduced during molding increases, resulting in an increase inyellowness. On the other hand, in the case where the polymerizationtemperature and the mixing temperature are high, the reaction rateincrease, and the amount of remaining OH groups derived from monomersdecreases, but the amount of vinyl groups occurring in the reactionsystem increases, and the yellowness tends to be high. In contrast,according to the method of the present invention, the production of bothof compounds having aliphatic terminal OH groups and compounds havingvinyl terminal groups in the resin compositions can be suppressed, as aresult of which resin compositions in which coloration is suppressed canbe obtained.

Further, the resin compositions of the present invention maintainfluidity, thus having excellent moldability, and therefore it can besaid that they are suitable as materials for precision members.

2. Film

Using the resin compositions produced above, films were produced. Theobtained films were evaluated by the methods shown below.

(1) Total Light Transmittance and Haze

The total light transmittance and haze were measured using a haze meter(“HM-150” manufactured by MURAKAMI COLOR RESEARCH LABORATORY) accordingto JIS K-7361 and JIS K-7136.

(2) Glass Transition Temperature

The measurement was performed using a differential thermal scanningcalorimeter (DSC) (measurement device: Hitachi High-Tech ScienceCorporation DSC7000X).

(3) Surface Shape

The surface shapes of the light diffusing films were evaluated based onthe arithmetic average roughness. The arithmetic average roughness wascalculated as follows, by plotting a roughness curve using a smallsurface roughness meter (“Surftest SJ-210” manufactured by MitutoyoCorporation). From the plotted roughness curve, the range of thereference length (l) (average line direction) was extracted. When theaverage line direction of the extracted portion serves as the X axis,the direction orthogonal to the X axis serves as the Y axis, and theroughness curve is expressed as y=f(x), a value (μm) obtained by thefollowing expression was taken as arithmetic average roughness (Ra).Here, the “reference length (1) (average line direction)” indicates thereference length of roughness parameters based on JIS B 0601:2001(ISO4287:1997).

${Ra} = {\frac{1}{\ell}{\int_{0}^{\ell}{{{f(x)}}{dx}}}}$(4) Refractive Index

Films having a thickness of 0.1 mm were measured using an Abberefractometer according to the method of JIS-K-7142 (at a wavelength of589 nm at 23° C.).

(5) Abbe Number (ν)

The refractive index of a film having a thickness of 0.1 mm was measuredusing an Abbe refractometer at a wavelength of 486 nm, 589 nm, and 656nm, at 23° C., and further the Abbe number was calculated using thefollowing expression.ν=(nD−1)/(nF−nC)

-   nD: Refractive index at a wavelength of 589 nm-   nC: Refractive index at a wavelength of 656 nm-   nF: Refractive index at a wavelength of 486 nm-   (6) Melt Volume Rate (MVR)

The MVR is an index indicating the fluidity of the resin compositions,and a larger value indicates a higher fluidity. The resin compositionsproduced in Examples were dried at 120° C. under vacuum for 4 hours, andthe measurement was performed using a melt indexer T-111, manufacturedby Toyo Seiki Seisaku-sho, Ltd., under conditions of a temperature of260° C. and a load of 2160 g.

Example 5

Pellets of the resin composition produced in Example 2 weremelt-extruded at 280° C. using a 26-mm twin screw-extruder and a T-die.The extruded molten film was nipped with a first cooling roll having adiameter of 200 mm and made of silicon rubber and a matted (arithmeticaverage surface roughness: 3.2 μm) second cooling roll having a diameterof 200 mm and made of metal. The matte pattern was shaped on the filmsurface, followed by cooling, and further the film was passed on a thirdcooling roll having a mirror surface structure and made of metal, sothat a single sided matte film was formed while being taken up with atake-up roll. At this time, the arithmetic average roughness of the filmsurface was adjusted to 3.0 μm by setting the temperature of the firstcooling roll to 40° C., the temperature of the second cooling roll to130° C., and the temperature of the third cooling roll to 130° C., andadjusting the speed of the cooling rolls.

Comparative Example 3

Using pellets of a polycarbonate resin (EUPILON H-4000, manufactured byMitsubishi Engineering-Plastics Corporation), a film was produced in thesame manner as in Example 5.

The evaluation results for the films obtained in Example 5 andComparative Example 3 are shown in Table 2.

TABLE 2 Comparative Example 5 Example 3 Film thickness (μm) 220 250 Haze(%) 88.6 76 Total light transmittance (%) 86.1 89.1 Arithmetic averageroughness (μm) 3.0 1.8 Glass transition temperature (° C.) 134 142 MVR260° C. cm³/10 min 32 30 Abbe number 21.5 30.1 Refractive index 1.6511.584

The films of the present invention exhibit high haze and high arithmeticaverage roughness while maintaining the total light transmittancerequired for optical films. This means that the films of the presentinvention have excellent transferability, that is, excellentshapability. Further, it also turns out that the films of the presentinvention are excellent in evaluation of the Abbe number, the refractiveindex, and the like, that are required as basic properties of opticalmaterials. Further, the films of the present invention have small valuesof the birefringence phase difference. This means that the difference inbirefringence between the center and the ends of the films is small, andthe films are more uniform.

It should be understood that some embodiments of the invention describedherein are intended for purposes of illustration only and are notintended to limit the scope of the invention. These novel embodimentscan be embodied in various other forms, and various omissions,replacements, and changes can be made without departing from the scopeof the invention. These embodiments and their modifications would fallwithin the scope and spirit of the invention and are included in theinvention described in the appended claims and their equivalents.

The invention claimed is:
 1. A method for producing a resin composition,comprising: (a) obtaining a resin by polymerization of a resin rawmaterial containing a compound represented by formulas (1) and (3), inwhich formula (1) is:

wherein R₁ and R₂ is each independently selected from a hydrogen atom,an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, acycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and ahalogen atom; each X is independently an optionally branched alkylenegroup having 2 to 6 carbon atoms; and each n is independently an integerof 1 to 5; and formula (3) is:

wherein each Z is independently an optionally branched alkylene grouphaving 2 to 6 carbon atoms; and each m is independently an integer of 1to 5; and (b) obtaining a resin composition by mixing an additive intothe resin, wherein a polymerization temperature T1 in step (a) fallswithin the range of 230° C. <T1 <250° C., and a mixing temperature T2 instep (b) falls within the range of 250° C. T2 <280° C., an amount ofaliphatic terminal OH groups by the calculated using the followingexpression is 0.2 or less, based on the ¹H-NMR spectra of the resincomposition${{Amount}\mspace{14mu}{of}\mspace{14mu}{aliphatic}\mspace{14mu}{terminal}\mspace{14mu}{OH}\mspace{14mu}{groups}} = {\frac{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 2.02\mspace{14mu}{to}\mspace{14mu} 1.95\mspace{14mu}{ppm}}{{Integral}\mspace{14mu}{value}\mspace{14mu}{of}\mspace{14mu}{peaks}\mspace{14mu}{at}\mspace{14mu} 7.83\mspace{14mu}{to}\mspace{14mu} 7.65\mspace{14mu}{ppm}}.}$2. The method according to claim 1, wherein the polymerization isperformed under a pressure of 1 Torr or less.
 3. The method according toclaim 1, wherein X is ethylene.
 4. The method according to claim 1,wherein n is
 1. 5. The method according to claim 1, wherein the compoundrepresented by formula (1) is selected from the group consisting of9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.
 6. The methodaccording to claim 1, wherein the resin further contains a structuralunit derived from a compound represented by formula (2) below:

wherein R₆ and R₇ are each independently selected from a hydrogen atom,an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, acycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and ahalogen atom; each Y is independently an optionally branched alkylenegroup having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10carbon atoms, or an arylene group having 6 to 10 carbon atoms; W is asingle bond or

wherein R₈, R₉, and R₁₄ to R₁₇ are each independently selected from ahydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an arylgroup having 6 to 10 carbon atoms; R₁₀ and R₁₁ are each independentlyselected from a hydrogen atom and an alkyl group having 1 to 5 carbonatoms; R₁₂ and R₁₃ are each independently selected from a hydrogen atom,an alkyl group having 1 to 5 carbon atoms, and a phenyl group; and Z′ isan integer of 3 to 11; and p and q are each independently an integer of0 to
 5. 7. The method according to claim 6, wherein p and q are 0, and Wis:


8. The method according to claim 6, wherein the compound represented byformula (2) is bisphenol A.
 9. The method according to claim 1, whereinZ is ethylene.
 10. The method according to claim 1, wherein m is
 1. 11.The method according to claim 1, wherein the compound represented byformula (3) is 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene.
 12. Themethod according to claim 1, wherein the resin is selected from thegroup consisting of a polycarbonate resin, a polyester resin, and apolyester carbonate resin.
 13. The method according to claim 12, whereinthe resin is a polycarbonate resin.